Method for making particulate amine-functionalized polyaryletherketone polymers and copolymers thereof

ABSTRACT

The present invention provides a method of preparing an amine-functionalized (e.g. amine-terminated) polyaryletherketone polymer, or imide- or sulphone-copolymer thereof and amine-protected analogues thereof, said method comprising the step of polymerizing a monomer system in a reaction medium comprising a capping agent comprising —NR 2 , —NRH or a protected amine group.

The present disclosure concerns functionalised (e.g.amine-functionalised) polyarylether ketones (PAEKs or PEKs). Inparticular, it concerns methods for making the reactive PAEKs, forexample using an electrophilic process in which the reactive end-cap isprotected during the reaction and subsequently de-protected during thefinal work-up.

Common terminology involves naming such polymers by reference to thestructure of the repeating unit (as is standard in polymer chemistry)with families being named according to the sequence of ether (symbolisedby “E”) and ketone (symbolised by “K”) linkages in the repeat units. Forexample, polymers consisting essentially of the repeating unit:—Ar—O—Ar—C(═O)—Ar—C(═O)— would be referred to as “PEKK”.

Polyarylether ketones (or “PEKs) have a variety of useful properties,such as excellent electrical insulating and mechanical properties athigh temperature, high strength, toughness and resistance to heat andchemicals. Such polymers may be amorphous or semi-crystalline. Bothtypes usually exhibit high glass transition temperatures (T_(g)), whilethe semi-crystalline forms also exhibit high melting temperatures(T_(m)). Amongst these polymers, the PEK, PEKK, PEEK, PEEKK and PEKEKKfamilies are of particular interest for use in preparing biomedicalimplants and implant materials due to their excellent mechanicalproperties, chemical inertness and resistance to stress cracking. Thesame materials are also useful in aerospace and many other wide-rangingindustrial applications including the preparation of thermoplasticcomposites.

The production of amino-terminated PEEK is described in Corfield et al.(“Synthesis and Colorimetric curing study of Amino-terminated PEEKoligomers” J. Polymer Sci. (1992) 30:845-849). This polymer is producedvia a nucleophilic process in which a meta-aminophenol end-capper isused to terminate the linear polymer chains. The purpose of producingthis polymer was to study the behaviour of the system on curing.Specifically, it was found that thermal cross-linking produced a highlycross-linked and amorphous solid. There is no suggestion in Corfieldthat there would be any particular benefits to using amino-terminatedPEEK or that the process could be extended to other PAEKs.

An improved process for the production of PEKK is described in WO2011/004164 (Ketonex). This process is electrophilic (i.e. aFriedel-Crafts process) and uses a Lewis acid and a controlling agentsuch as benzoic acid. This dispersion process can yield particles of aPEKK product having a uniform shape and a controllable sizedistribution. WO '164 is silent as to the use of capping agents otherthan those having phenyl or chlorophenyl end-groups and provides noteaching towards incorporating functionalised end-caps into PEKK.

As noted above, PAEKs have wide-ranging uses due to their excellentmechanical properties, chemical inertness and resistance to stresscracking. However, some applications of the polymers would benefit fromfurther functionality. There thus exists a need for functionalised PAEKsand methods for their preparation.

The present inventors have surprisingly found that amine-functionalised(e.g. amine-terminated) PAEKs can be produced using a process in whichthe reactive amine end-cap is protected during the reaction andsubsequently de-protected during the final work-up. The invention thusconveniently enables the addition of amine groups when performing thepolymerisation reaction, i.e., no additional steps are required on orderto achieve amine functionalisation. The use of protecting groups iscommon in pharmaceutical organic chemistry, but is generally avoided inpolymer chemistry and other industrial applications due to theadditional cost and complexity it can add to a process.

Thus, viewed from a first aspect, the present disclosure providesamine-functionalised (e.g. amine-terminated) polyaryletherketonepolymers, or imide- or sulphone copolymers thereof and amine protectedanalogues thereof in particulate form, i.e. particles of anamine-functionalised (e.g. amine-terminated) polyaryletherketonepolymer, or imide- or sulphone copolymer thereof and amine protectedanalogues thereof.

Preferably, the particulate polymers of the present disclosure areparticles of an amine-functionalised polyaryletherketone polymer orcopolymer thereof, said polymer or copolymer having an inherentviscosity (IV) of at least 0.28 dl/g, particularly in the range of0.4-1.7 dl/g, and in some embodiments, the IV is in the range of 0.6-1.5dl/g,

-   -   wherein said amine-functionalised polyaryletherketone polymer or        copolymer thereof is selected from the group consisting of:        polyaryletherketone polymer with terminal amine or protected        amine functional group(s); polyaryletherketone-imide copoplymer        with terminal amine or protected amine functional group(s); and        polyaryletherketone-sulphone copolymer with terminal amine or        protected amine functional group(s). The particles may be        substantially spherical in shape or rod shaped.    -   In some embodiments, the particles are substantially spherical        in shape with an aspect ratio (R) of about 1 to 1.5 or rod        shaped with an aspect ratio 1.5 to 10 (where R=a/b, “a” is the        largest dimension, and “b” is the smallest dimension).

Viewed from a further aspect, the particulate polymers of the presentdisclosure are particles of an amine-functionalised polyaryletherketonepolymer or copolymer thereof, said polymer or copolymer having a weightaverage molecular weight (Mw) of at least 8,000, preferably greater than10,000, an inherent viscosity of at least 0.28 dl/g, and a glasstransition temperature of at least 140° C. as measured by differentialscanning calorimetry,

-   -   wherein said amine-functionalised polyaryletherketone polymer or        copolymer thereof is selected from the group consisting of:        polyaryletherketone polymer with terminal amine or protected        amine functional group(s); polyaryletherketone-imide copoplymer        with terminal amine or protected amine functional group(s); and        polyaryletherketone-sulphone copolymer with terminal amine or        protected amine functional group(s), and    -   wherein said particles are substantially spherical in shape with        an aspect ratio (R) of about 1 to 1.5 or rod shaped with an        aspect ratio 1.5 to 10 (where R=a/b, “a” is the largest        dimension, and “b” is the smallest dimension).

The term “functionalised” is intended to encompass polymers with one ormore amine functional groups as end-groups. It also encompasses polymersin which the amine groups are substituents on the polymer chain, i.e.pendant to the backbone. Preferably, the polymers are functionalised atthe end groups.

The polymers of the present disclosure can be produced using a processin which the reactive (nucleophilic) end-cap is protected during thereaction and subsequently de-protected during the final work-up.

The present disclosure therefore provides a method of preparing anamine-functionalised (e.g. amine-terminated) polyaryletherketonepolymer, or imide- or sulphone-copolymer thereof, said method comprisingthe step of polymerising a monomer system in a reaction mediumcomprising a capping agent comprising —NR₂, —NRH or a protected aminegroup. As this conveniently enables the addition of amine groups whenperforming the polymerisation reaction, the method is preferably asingle-step reaction, i.e., no additional steps before or afterpolymerisation are required in order to achieve amine functionalisation.

Preferably the process involves the use of a Lewis acid. Therefore,viewed from a further aspect, the present disclosure provides a methodof preparing an amine-functionalised (e.g. amine-terminated)polyaryletherketone polymer, or imide- or sulphone-copolymer thereof,

said method comprising the step of polymerising a monomer system in areaction medium comprising:

-   -   (a) a Lewis acid; and    -   (b) a capping agent comprising —NR₂, —NRH or a protected amine        group.

Particularly preferably, the process further involves a controllingagent. Thus, viewed from one aspect, the present disclosure provides amethod of preparing an amine-functionalised (e.g. amine-terminated)polyaryletherketone polymer, or imide- or sulphone-copolymer thereof,said method comprising the step of polymerising a monomer system in areaction medium comprising:

-   -   (a) a Lewis acid;    -   (b) a controlling agent and    -   (c) a capping agent comprising —NR₂, —NRH or a protected amine        group.

“R” is either an aliphatic or aromatic group and is defined below.

Preferably the controlling agent comprises an aromatic carboxylic acid,an aromatic sulphonic acid, or a derivative thereof or a Lewis base.

The functionalised polyaryletherketones of the present disclosure arepolymers comprising the unit—Ar—O—Ar—C(═O)—. They are characterised byaryl groups that are linked via ether, carbonyl (ketone), sulphone orimide groups and include, but are not limited to the following (andcombinations thereof):

-   -   Poly (ether ketone), i.e. PEK, a polymer consisting essentially        of the repeat unit: —Ar—O—Ar—C(═O)—.    -   Poly (ether ketone ketone), i.e. PEKK, a polymer consisting        essentially of the repeat unit: —Ar—O—Ar—C(═O)—Ar—C(═O)—.    -   Poly (ether ether ketone), i.e. PEEK, a polymer consisting        essentially of the repeat unit: —Ar—O—Ar—O—Ar—C(═O)—.    -   Poly (ether ether ketone ketone), i.e. PEEKK, a polymer        consisting essentially of the repeat unit:        —Ar—O—Ar—O—Ar—C(═O)—Ar—C(═O)—.    -   Poly (ether ketone ether ketone ketone), i.e. PEKEKK, a polymer        consisting essentially of the repeat unit:        —Ar—O—Ar—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)—.    -   Poly (ether ketone ketone), i.e. PEKK, is particularly        preferred.

Thus, preferably the polyaryletherketone polymers or copolymers of thepresent disclosure comprise one or more of the following aryletherketonerepeat units:

-   -   —Ar—O—Ar—C(═O)—    -   —Ar—O—Ar—C(═O)—Ar—C(═O)—    -   —Ar—O—Ar—O—Ar—C(═O)—    -   —Ar—O—Ar—O—Ar—C(═O)—Ar—C(═O)—    -   —Ar—O—Ar—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)—    -   wherein each Ar is independently an aromatic moiety.

Homopolymers of the above types are preferred, however, copolymers ofthe above repeat units with each other (e.g. PEKK-PEKEKK-PEKK) and withimide or sulphone units are also encompassed. Copolymers according tothe present disclosure include alternating, periodic, statistical,random and block copolymers.

References to polymers comprising a particular unit (e.g. anaryletherketone unit and optionally also an imide unit and/or a sulphoneunit) as herein described should be understood to encompass polymerscontaining one or more of said units or combination of units, as well aspolymers consisting of, or consisting essentially of, said units orcombination of units.

If desired, the polymers of the present disclosure may be blended withone another or with other types of polymer to form polymer blends.

Each aromatic moiety in the polymer repeating unit (Ar) may beindependently selected from substituted and unsubstituted mononucleararomatic moieties (e.g. phenylene) and substituted and unsubstitutedpolynuclear aromatic moieties. The term “polynuclear” is considered toencompass fused aromatic rings such as naphthalene and non-fused ringssuch as biphenyl, etc. Particularly preferably, Ar is phenylene (Ph)e.g. unsubstituted phenylene.

The phenylene and polynuclear aromatic moieties (i.e. “Ar”) may containsubstituents on the aromatic rings. Such substituents would be readilyunderstood by the skilled person and should not inhibit or otherwiseinterfere with the polymerisation reaction to any significant extent.Typical substituents may include, for example, phenyl, halogen (e.g. F,Cl, Br, I), ester, nitro, cyano and the like.

In cases where Ar is substituted, the substituents are preferablypendant to the chains, rather than in the backbone, i.e. not bonded to acarbonyl carbon atom of a ketone linkage nor to an oxygen atom of anether linkage. Thus, in a particularly preferred aspect, the ketonelinkages (i.e. the carbon atoms of the carbonyl group) are directlyattached to carbon atoms, especially to carbon atoms of adjacentaromatic (i.e. to aromatic carbons). Similarly, the oxygen atoms of theether linkages are preferably attached to carbon atoms, especially toaromatic carbon atoms of adjacent aromatic groups.

The polymers of the present disclosure are “functionalised” insofar asthey comprise one or more amine groups as end groups, i.e. at one ormore ends of the polymer chain and/or as pendant groups, i.e. at one ormore positions along the polymer backbone. With regard to particulatepolymers of the present disclosure, the term “functionalised” istherefore intended to encompass amine groups on the particles, at leastsome of which have the potential to bond with other materials, e.g.other monomers in formulations.

The functional groups for the polymers of the present disclosure areamines, i.e. —NR₂, NRH or —NH₂, preferably NRH or —NH₂, especially —NH₂,and derivatives thereof, where “R” is either an aliphatic or aromaticgroup. Where R is an aromatic group, it is preferably Ar as hereindescribed (especially phenyl). Where R of —NR₂ or NRH is an aliphaticgroup, it is preferably selected from alkyl groups, e.g. C1-6 aliphaticgroups, especially methyl or ethyl groups. The compounds describedherein in which the functional group is protected, i.e. thosefunctionalised by protected amine groups as described herein, form afurther aspect of the present disclosure.

Multiple amine functionalisation is also encompassed, e.g. where aphenyl ring at the end of the polymer has more than one, i.e. 1 to 5amine groups thereon.

Preferably, the polymers of the present disclosure are terminated withan amine group, i.e. an amine group is found on at least one end of thepolymer chain. Typically at least 50% of the end groups, i.e. the endsof the polymer chains are amine-functionalised, preferably at least 70%,especially preferably at least 85%, e.g. at least 95%. Preferably,substantially all chain ends comprise an amine group. Amine-terminatedpolymers are particularly preferred.

In a further aspect, as an alternative to, or in addition, toamine-termination of the chain, the amine groups may be pendant to thepolymer chain, i.e. they are substituents of the polymer's aromaticmoieties. Typically, 0 to 100% of the Ar groups, preferably 25 to 75%,i.e. around 50% of the Ar groups are substituted with an amine group.

The amine groups of the present disclosure may be situated on arylgroups which themselves are attached to ketone and/or ether linkages ofthe polymer. In a less preferred aspect, there may be a linker groupbetween the aryl group of the polymer chain and the amine group.

Linear polymers are preferred, however cross-linked polymers are alsoencompassed. Cross-linked polymers may be produced by usingcross-linking agents and/or suitable monomers containing more than two(i.e. 3, 4, 5 or 6) ether or carboxylic acid halide (e.g. chloride)groups in the methods of the present disclosure. Examples of suchmonomers and agents include benzene-1,3,5-tricarbonyl chloride;1,3,5-triphenoxy benzene; benzene-2,3,5,6-tetracarbonyl chloride;benzene-1,2,3,4,5,6-hexacarbonyl chloride; 1,2,3,4,5,6-hexaphenoxybenzene; naphthalene-1,4,5,8-tetracarbonyl chloride, triphenoxybenzene,benzenetricarboxylic acid chloride, hexaphenyl benzene and the like.These monomers or agents are typically used in relatively lowconcentrations, e.g. from 0.5M % to 25M %, or between 0.5M % and 25M %.

Especially preferably the compounds of the present disclosure are linearand terminated with a functional group. Particularly preferred compoundsare those according to the following formulae (and imide- orsulphone-copolymers thereof):

E-[-Ar—O—Ar—C(═O)-]_(n)-E

E-[-Ar—O—Ar—C(═O)—Ar—C(═O)-]_(n)-E

E-[-Ar—O—Ar—O—Ar—C(═O)-]_(n)-E

E-[-Ar—O—Ar—O—Ar—C(═O)—Ar—C(═O)-]_(n)-E

E-[—Ar—O—Ar—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)-]_(n)-E

where n is an integer from 1 to 200, e.g. 15 to 200 or 20 to 200,especially 30 to 150, particularly preferably 30 to 60, e.g. around 40or 50 and E is an amine functional group as herein described, especially—NH₂.

In a particularly preferred aspect, the functionalised polymer orcopolymer of the present disclosure has the following structure:

where E is an amine functional group or protected amine, preferably NH₂,as described herein and n is as described above, preferably 15 to 200.

Amine-functionalised monomers and oligomers form a further aspect of thepresent disclosure. Thus, viewed from a further aspect, the presentdisclosure provides oligomer derivatives of the polymers and copolymersherein described, e.g. amine-functionalised (e.g. amine-terminated)aryletherketone monomers or oligomers, or imide- or sulphone-derivativesthereof. Where more than one ether-ketone unit is present, the compoundmay be monofunctional, bifunctional, trifunctional or multifunctional.

Particularly preferred monomer/oligomer compounds are those according tothe following formulae (and imide- or sulphone-derivatives thereof):

-   -   E-[-Ar—O—Ar—C(═O)-]_(n)-E    -   E-[-Ar—O—Ar—C(═O)—Ar—C(═O)-]_(n)-E    -   E-[—Ar—O—Ar—O—Ar—C(═O)-]_(n)-E    -   E-[—Ar—O—Ar—O—Ar—C(═O)—Ar—C(═O)-]_(n)-E    -   E-[—Ar—O—Ar—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)-]_(n)-E    -   where n is an integer from 1 to 20, e.g. 1 to 10, especially 1        to 5, particularly preferably 2 to 4 and E is an amine        functional group or protected amine as herein described,        especially —NH₂, especially wherein the compound is obtained or        obtainable by a method comprising the step of reacting a monomer        system in a reaction medium comprising:    -   (i) a capping agent comprising —NR₂, —NRH or a protected amine        group.    -   (ii) a Lewis acid and    -   (iii) and a controlling agent comprising an aromatic carboxylic        acid, an aromatic sulphonic acid, or a derivative thereof.

Especially preferred monomers/oligomers according to the presentdisclosure are the following:

The functionalised compounds of the present disclosure are producedusing a process which involves use of a capping agent. The capping agentcomprises —NR₂, —NRH or a protected version of the amine group which isintended to functionalise the polymer, copolymer, monomer or oligomer.Certain protected capping agents are novel and form a further aspect ofthe present disclosure. Preferably, the capping agent comprises aprotected amine group.

Without wishing to be bound by theory, it is thought that, if notprotected, then any amine groups (especially those comprising —NH₂)involved in the polymerisation reaction would react with the carboxylicacid chloride monomers to give an amide linkage in the polymer chainthat is unstable compared to a ketone group. The capping agents of thepresent disclosure therefore comprise, e.g. include, —NR₂, NRH orprotected amine functional groups (preferably protected amine groups),the protecting group functioning to protect the eventual amine groupsduring polymerisation. The use of a capping agent comprising —NR₂, —NRHor a protected amine, in the production of the polyaryletherketones andtheir copolymer, monomer and oligomer analogues herein described isnovel and thus forms a further aspect of the present disclosure. Cappingagents comprising leaving groups (e.g. those comprising protected aminegroups) are especially preferred. Capping agents comprising hydroxylgroups (—OH) are less preferred.

Especially suitable capping agents of the present disclosure are ofgeneral formula (Z)_(a)—Ar—(X)_(b) wherein:

-   -   each X is independently selected from —O—Ar, —C(═O)Cl,        —C(═O)—Ar—O—Ar and —O—Ar—[—C(═O)—Ar—O—Ar-]_(c-)H where each Ar        is independently as defined herein;    -   c is an integer, e.g. 1 to 10, preferably 1 to 4,    -   Z is —NR₂, —NRH or a protected amine group, e.g. each Z is        independently selected from —NR₂, —NRH, —NHL, —NRL or —NL₂        (preferably —NHL) and L is a leaving group, such as an acetyl,        haloacetyl (e.g. trifluoroacetyl), carbonate (e.g. t-Boc),        sulphonyl, halosulphonyl, —SO₂—R, e.g. —SO₂—CH₃, —SO₂—CF₃ etc.        (carbonate groups such as t-Boc are less preferred);    -   each R group is independently as defined herein, i.e. an        aliphatic or aromatic group;    -   a is 1 to 5, preferably 1, 2 or 3, especially 1 and    -   b is 1 to 5, preferably 1, 2 or 3, especially 1.

In one embodiment, where Z is NL₂, the two leaving groups can be linkedto form an imide, e.g. Z is of the following structure:

Where Y is a linker group, especially an aryl group (especially phenyl),—(CH₂)_(n)— or —(CF₂)_(n)—, where n is an integer, preferably 2 to 6. Apreferred capping agent of this type is the following, which isavailable from Molport.

Where R is an aromatic group, it is preferably Ar as herein described(especially phenyl). Where R is an aliphatic group, it is preferablyselected from alkyl groups, e.g. C1-6 aliphatic groups, especiallymethyl or ethyl groups.

In the case where the capping agent comprises —NR₂ or —NRH, each R groupis independently as defined herein, i.e. R is independently selectedfrom an aliphatic or aromatic (e.g. Ph) group, preferably aliphatic, e.g. alkyl groups, e.g. C1-6 aliphatic groups, especially methyl or ethylgroups.

Preferably, the capping agent is of formula Z-Ph-O-Ph.

Particularly preferably, Z is a haloacetyl protected amine group, e.g.—NH_(n)R, especially, a trifluoroacetamide group.

Preferred capping agents include the following compound and its acetylequivalent, i.e. compounds of the above formula where n is 1, Ar is Phand R is acetyl or trifluoroacetyl:

-   -   (Referred to as CF₃-EC or        2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide)

The trifluoroacetyl group has been found to be particularly easy toremove during the acid/base work-up.

Other preferred capping agents include H₃C—C(═O)N(H)PhC(═O)Cl, protected3,5-diaminodiphenylether and derivatives thereof.

The capping agents of the present disclosure can be prepared fromreadily available materials such as aminobenzoic acid, diaminobenzoicacid and diphenylether.

While the functional groups of the present disclosure are preferablypresent at the chain end of the compound, functionality pendant to thechain is also an aspect of the present disclosure. In this case, ratherthan a capping agent (which adds functionality to the end of the chains)a functionalised monomer is used. The amine functional group of themonomer must be protected in order to avoid unstable amide linkagesbeing formed. Suitable monomers are iso- or tere-phthalic acid chloridescomprising protected amine groups as described above. For example, theamine group of 5-aminoisophthalic acid may be protected prior toconversion of the molecule to the acid chloride. This can then be usedin place of some of the terephthaloyl or isophthaloyl chloride monomerswhen preparing the PAEKs of the present disclosure.

An advantageous feature of the processes of the present disclosure isthat the leaving group of the capping agent (i.e. L) is removed duringstandard work-up procedures following the polymerisation. There is thusno need for a separate “deprotection” step.

Typical work-up conditions which result in removal of the leaving groupare the use of water, or acidic/basic aqueous solutions, e.g. solutionsof HCl or NaOH. The water or solution is typically at a temperature of 0to 100° C. at atmospheric pressure, preferably 20 to 100° C., e.g. 50 to80° C. In some aspects, work-up can take place under pressurisedconditions, e.g. at pressures of 200 kPa.

A representative workup procedure for a PEKK polymerisation carried outin a one litre reactor is as follows:

-   -   Stand in deionised water overnight;    -   Filtered and slowly added to 1.5 litres of stirred, hot        deionised water to remove the residual dichloromethane    -   1.5 litres of deionised water and 100 ml concentrated        hydrochloric acid are added, boiled for 1 hour, filtered, washed        with 500 ml deionised water, filtered;    -   1.5 litres of deionised water, boiled for 1 hour, filtered,        washed with 500 ml deionised water, filtered;    -   1.5 litres deionised water made to pH 13 with ammonia solution        (˜30 ml), boiled for 1 hour, filtered, washed with 500 ml        deionised water, filtered;    -   1.5 litres deionised water, boiled for 1 hour, filtered, washed        with 500 ml deionised water, filtered; Off-white PEKK powder        isolated.

The monomer system used in the methods herein described comprisesmonomers suitable for polymerisation or co-polymerisation in order toproduce a polyaryletherketone, or imide- or sulphone-copolymer thereof.Such monomer systems and combinations would be readily apparent to theperson skilled in the art.

Preferred monomers may include but are not restricted to:

Preferably, at least one of R1 and R3 is the branch unit:

Where branched units are present, they are preferably present in a molarpercentage of 0.5% to 25% (i.e. 0.5 to 25 M %).

Preferred monomers may include iso and terephthaloyl halides andphthaloyl halides (i.e. the 1,2 substituted version), preferably iso andterephthaloyl halides, preferably chlorides and1,4-bis(4-phenoxybenzoyl)benzene.

Especially preferred monomers are the following:

TPC

IPC

NAC (numbers will give the positions of the substitution e.g 2,6 or 1,4)

EKE

ESE

EKKE

EIEIE

EIKIE

EISIE

EI-IE

EI6FIE

EINIE

EKNKE

Preferred monomers for the production of the copolymers of the presentdisclosure include the following (i.e. the copolymer comprises anaryletherketone repeat unit and one or more of the following repeatunits):

It has been found that those PEK-Imide copolymers that have electronwithdrawing groups between the imide units (—C(═O)— and —SO₂—) canresult in the products being melt unstable at certain processingtemperatures. This can also be the case where the imide unit is in theform -imide-C₆H₂-imide-. Preferably R₂ in the above formula is thereforeeither electron donating or electron neutral, e.g. a bond, ether, or—C(CF₃)₂— as these have been found to be the most stable.

In an especially preferred aspect of processes of the present disclosurefor making copolymers, the reaction medium comprises, in addition to theLewis acid, the controlling agent and capping agent, a compoundcomprising an aromatic moiety and more than one reactive carbonyl group(e.g. more than one carboxylic acid halide group). In some aspects, thiscompound can be used as an alternative to the monomer system suitablefor forming aryletherketone linkages. Such compounds facilitate reactionbetween the aryletherketone and non-aryletherketone components of thecopolymers and are especially preferred where one or more of themonomers are not self-polymerising. Suitable compounds includemultifunctional (especially difunctional or trifunctional) aromaticcarboxylic acid halides, especially aromatic di- or tri-carboxylic acidhalides, e.g. one or more of the following (where Cl is preferred butmay be replaced by any other halide):

Particularly preferred compounds for this aspect are iso andterephthaloyl halides, preferably chlorides. This aspect of the presentdisclosure is especially preferred where one or more of the monomers isnot self-polymerising as the ketone groups of the monomer participate inthe reaction.

Whilst the above-listed chlorides are preferred, other acid halides,particularly the fluorides and the bromides, may also be used.Generally, the chlorides are preferred due to their availability andreactivity. Other groups that are potentially displaceable underFriedel-Crafts conditions may also be used.

These might include groups such as —OR, where R is methyl, ethyl,isopropyl or other lower alkyl.

The combinations of monomers suitable for producing the polymermaterials herein described would be readily apparent to a person skilledin the art, as would the relative proportions of the monomers.

Self-condensing monomers such as Ph-O-Ph-C(═O)—Cl (4-phenoxybenzoylchloride) and Ph-O-Ph-N(C═O)₂Ph-C(═O)Cl, i.e.:

are also suitable. For example, monomers with repeating units “EKK” canbe polymerised alone, i.e. without a co-monomer, to produce PEKK.

The proportion of 1,4-linked aromatic (e.g. phenyl) rings inpolyaryletherketones greatly influences the characteristics of theresulting polymer and the size of the particles formed (e.g. itsprocessability, glass transition temperature and its crystalline meltingpoint, even to the extent of producing an amorphous PEKK etc.).Depending on the intended use for the polymer produced, thecharacteristics can be modified by changing the proportion of 1,4-linkedaromatic rings in the polymer. This may be achieved by the use ofmonomers comprising 1,3-substituted aromatic rings. For example,isophthaloyl halides such as isophthaloyl chloride can be used asmonomers and the amounts chosen in relation to the other monomers inorder to produce a polymer with the desired characteristics. Preferablythe monomers are chosen such that the proportion of 1,3-linked aromaticrings in the resulting polymer is 0 to 100%, more especially 0 to 50% or0 to 40%, e.g. 5 to 50%, particularly 20 to 40%, e.g. about 30%. Allpercentages and ratios are by weight, unless otherwise specified. Theproportion of 1,4 (tere-, or “T”) to 1,3 (iso-, or “I”)-linked aromaticrings in the resulting polymer can also be represented as a tere-:iso-,or “T:I” ratio and is preferably within the range of 100:0 to 60:40.

Particularly preferably the monomer system comprises bis1,4-(4-phenoxybenzoyl)benzene and terephthaloyl halide and isophthaloylhalides (e.g. a 60:40 mixture of tere- and iso-phthaloyl chloride) in a1:1 ratio by weight. This would produce an 80:20 PEKK polymer, i.e. theiso-linked units would be present in 20% by weight in the final polymermaterial.

The ratio (e.g. molar ratio) of aryletherketone units tonon-aryletherketone units (i.e. sulphone or imide groups) in thecopolymers and oligomers of the present disclosure is in the range of1:99 to 99:1, e.g. 20:80 to 80:20, especially 30:70 to 70:30, 40:60 to60:40 or 50:50. The most preferable ratios are 30:70 and 70:30.

The temperature at which the reaction is conducted can be from about−50° C. to about +150° C. It is preferred to start the reaction at lowertemperatures, for example at about −50° C. to about −10° C.,particularly if the monomer system contains highly reactive monomers.After polymerisation has commenced, the temperature can be raised ifdesired, for example, to increase the rate of reaction. It is generallypreferred to carry out the reaction at temperatures in the range ofbetween about −30° C. and +25° C., particularly +20° C.

The fact that the processes of the present disclosure can be carried outat relatively low temperatures renders the present disclosure areparticularly useful for the production of block copolymers as the two(or more) types of monomer can be added sequentially by opening thereactor once the first component has reacted. The high temperatures(e.g. 350° C.) required for nucleophilic processes render this openingof the reactor problematic (e.g. for safety reasons), the lowtemperature processes of the present disclosure solve this problem.Having calculated the monomer ratios for block length required (e.g. fora PEKK block, the EKKE monomer to KK monomer ratio), the first monomersystem is polymerised (preferably in the presence of the Lewis acid andthe controlling agent). After that has been given a suitable amount oftime to polymerise, which, using the processes of the present disclosurecan be carried out at +20° C., the other monomers can be added(following optional cooling to e.g. +5° C.). Addition of furthermonomers is ideally carried out gradually so as to prevent the reactiontemperature rising excessively.

For the production of copolymers, the monomer system suitable forforming aryletherketone units is polymerised before, after, or at thesame time as, the comonomer (i.e. the unit or units which form thenon-aryletherketone units of the copolymers of the present disclosure).Moreover, the monomer system suitable for forming aryletherketone unitsmay be polymerised in the same vessel or a different vessel topolymerisation of the comonomer For the formation of random copolymers,all types of monomer may be added and/or polymerised together, i.e. theyare polymerised simultaneously in the same vessel. For the formation ofblock copolymers, the types of monomer are polymerised separately, e.g.at different times and/or in different vessels. For example, at leastone type of monomer is added after at least one other has polymerised,e.g. the monomer system suitable for forming aryletherketone units ispolymerised before or after the comonomer (or vice versa).Alternatively, in an embodiment especially suited to the formation ofblock copolymers, the monomers for forming aryletherketone units andthose for forming non-aryletherketone units comonomer (i.e. the imideand/or sulphone monomer) are polymerised in different vessels and thenmixed together to form the copolymers of the present disclosure.

Thus, in a preferred aspect, the monomer system suitable for formingaryletherketone units is polymerised before the comonomer (i.e. theimide and/or sulphone monomer) is added to the reaction medium, or thecomonomer is polymerised before the monomer system suitable for formingaryletherketone units is added to the reaction medium. In a furtheraspect, the monomers are polymerised in different vessels prior tomixing to form the copolymers of the present disclosure.

In one aspect of the present disclosure (particularly for the productionof copolymers), the monomer system suitable for forming aryletherketoneunits may be replaced by one or more monomers which consists essentiallyof aryl and ketone groups or consists essentially of aryl and ethergroups, preferably one consisting of aryl and ketone groups, especiallya “KK” unit such as a phthaloyl halide as herein described. In such anaspect the comonomer which comprises non-aryletherketone units shouldcontain ether linkages such that the eventual copolymer contains bothether and ketone linkages.

Preferably, the method of the present disclosure employs a controllingagent. Preferably, the controlling agent is a Lewis base or an aromaticcarboxylic acid, aromatic sulphonic acid or derivatives thereof.

Where the controlling agent is an aromatic carboxylic acid, aromaticsulphonic acid or derivatives thereof, such acids may comprise 1, 2 or 3carboxylic or sulphonic acid groups on an aromatic ring (i.e. these maybe mono-, di- or tri-acids). Derivatives of such acids include metalssalts and esters.

Preferred controlling agents for use in the method of the presentdisclosure include the following:

-   -   (i) Ar′(COOX)_(y),    -   (ii) Ar′(SO₃X)_(y),    -   (iii) (Ar′COO⁻)_(z)M^(z+), or    -   (iv) (Ar'SO₃ ⁻)_(z)M^(z+)        wherein Ar′ is an aromatic group compatible with the remaining        components of the reaction medium;        each X independently is a hydrogen atom or an organic group (R);        each y independently is 1, 2 or 3;        each M independently is a metal ion and        each z independently is an integer equal to the charge on the        metal ion (M^(z+)).

The aromatic group of the controlling agent (i.e. Ar′) may be selectedfrom substituted and unsubstituted mononuclear (e.g. phenyl) andsubstituted and unsubstituted polynuclear aromatic moieties. Preferablythe aromatic group of the controlling agent is an optionally substitutedphenyl group. Preferred substituents may include halogen (e.g. F, Cl,Br, I), nitro, cyano, alkyl (e.g. 6 alkyl) and the like. Alkylsubstituents are preferred, e.g. methyl, ethyl, etc. Where substituentsare present, these are preferably electron-withdrawing groups whichdeactivate the ring to electrophilic attack.

When X=R, the organic group R is preferably a straight-chained orbranched C₁₋₆ alkyl group, i.e. the controlling agent is an alkyl esterof an aromatic carboxylic acid or aromatic sulphonic acid. Morepreferably, R is C₁₋₄ alkyl. e.g. methyl.

Especially preferred controlling agents for use in the presentdisclosure include benzoic acid, chlorobenzoic acid (e.g. 4-chlorobenzoic acid), methyl benzoic acid (e.g. 4-methyl benzoic acid), sodiumbenzoate, magnesium benzoate, aluminium benzoate, methyl benzoate andbenzene sulphonic acid. Particularly preferably, the controlling agentis benzoic acid.

Mixtures of two or more controlling agents may also be used, if desired.

In some aspects of the present disclosure the controlling agent is aLewis base. The term “Lewis base” refers to a substance capable ofdonating an unshared electron pair to a Lewis acid. Mixtures of two ormore Lewis bases can be used if desired.

Typical Lewis bases which can be employed include, amides, amines,esters, ethers, ketones, nitriles, nitro compounds, phosphines,phosphine oxides, phosphoramides, sulfides, sulfones, sulfonamides,sulfoxides and halide salts. More specifically, the Lewis base may beselected from acetone, benzophenone, cyclohexanone, methyl acetate,ethylene carbonate, N-methylformamide, acetamide, N,N-dimethylacetamide,N-methylpyrrolidone, urea, tetramethylurea, N-acetylmorpholine, dimethylsulfoxide, N,N-dimethylformamide, diphenyl sulfone,N,N-dimethylmethanesulfonamide, phosphoryl chloride, phenylphosphonylchloride, pyridine-N-oxide, triphenylphosphine oxide, trioctylphosphineoxide, nitropropane, nitrobenzene, benzonitrile, n-butyronitrile, methylether, tetrahydrofuran, dimethyl sulfide, trimethylamine,N,N,N′,N′-tetramethylethylenediamine, N,N-dimethyldodecylamine,imidazole, pyridine, quinoline, isoquinoline, benzimidazole,2,2′-bipyridine, o-phenanthroline, 4-dimethylaminopyridine etc. Inaddition to covalent organic compounds, suitable Lewis bases includeinorganic salts which can form complexes with Lewis acids, for example,chlorides, such as trimethylammonium chloride, tetramethylammoniumchloride, sodium chloride or lithium chloride, perchlorates,trifluoromethanesulfonates etc.

Particularly preferred Lewis bases are dimethylsulphone,N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide,1-methyl-2-pyrrolidone, tetramethylene sulfone (also known assulfolane), n-butyronitrile, dimethyl sulfide, imidazole, acetone,benzophenone, trimethylamine, trimethylamine hydrochloride,tetramethylammonium chloride, pyridine-N-oxide, 1-ethylpyridiniumchloride, lithium chloride, lithium bromide, sodium chloride, sodiumbromide, potassium chloride, potassium bromide and mixtures thereof.

The amount of controlling/dispersing agent present is preferably from0.1 to 6 equivalents per equivalent of acid halide groups present in themonomer system. Typical ranges of ratio of moles of controlling agent tomoles of acid halide groups present in the monomer system are from 0.1to 10, preferably 0.5 to 7, especially 0.7 to 5, particularly preferably1.5 to 2. Amounts greater than 5 equivalents could be employed, ifdesired, e.g. up to 10 equivalents, e.g. 7 equivalents. However, noadditional controlling or dispersing effect is usually achieved byadding larger amounts and it generally means that more Lewis acid isalso required. Thus, it is preferred to use no more than 5 equivalents,more preferably between 0.5 and 4 equivalents and especially 1 to 3 orbetween 0.5 and 2 or 2 to 4 (e.g. 2 to 3) equivalents per equivalent ofacid halide groups. A particularly preferred amount of Lewis basecontrolling agent is 1 equivalent per equivalent of acid halide groups,whereas for the carboxylic acid/sulphonic acid type controlling agent, 2equivalents per equivalent of acid halide groups are especiallypreferred.

The actual amount of controlling agent added depends upon, inter alia,the particular controlling agent used, the nature of the monomerspresent and the type and amount of Lewis acid employed. The ranges givenparticularly apply to the controlling agents containing one acid or baseacid functionality, e.g., those listed as (i) to (iv) above where y or zis equal to 1. For those controlling agents containing more than oneacid or base group per molecule, e.g. where y or z is not 1, theequivalents of controlling agent to acid halide groups in the monomersystems may be adjusted accordingly.

Many of the prior art polymerisation processes which employ controllingagents are unreliable to the extent that it cannot be predicted whethera complexed gel or dispersion will result. Mixed solvent systems havebeen used in order to promote dispersion over gel formation. Whilst suchsystems may be used in the methods herein described, this is notessential to achieve the desired effects. The present process thereforeallows the use of a single solvent (e.g. dichloromethane) which makessolvent removal easier; the dispersion of droplets is easier to control,e.g. benzoic acid can give dispersions of the polymer PEKK in puredichloromethane without the need for further diluents such ascyclohexane. The fact that solvent mixtures are not required makessolvent removal easier (e.g. dichloromethane can be distilled off at 41°C. with extremely high recovery rates). Use of a single solvent in theprocesses of the present disclosure is therefore preferred.

Moreover, controlling agents such as benzoic acid can also be readilyrecovered for future use when carrying out the methods of the presentdisclosure. The recovery of the controlling agent benzoic acid isfacilitated by the fact that the acid has very low solubility in coldwater but high solubility in hot water. Thus after heating the polymerslurry in water after decomplexation, the polymer can be recovered byfiltration and on allowing the filtrate to cool the benzoic acidcrystallises out facilitating its recovery for future use. Analternative method to recover the benzoic acid would be to addsufficient sodium hydroxide to form sodium benzoate which is watersoluble (1 g in 2 mL of water), filter and isolate the polymer and thenadd an acid such as hydrochloric acid to the filtrate to reform benzoicacid which would precipitate from the filtrate.

A further advantage of the present disclosure is the reduction in theamount of water necessary to remove the catalyst residues andcontrolling agents when compared to that necessary using the gel andtube process. In the complexed gel and tube process the polymer afterdecomplexation has a very low bulk density, sometimes as low as 0.08g/mL, thus requiring the use of large work-up vessels and largequantities of water to afford a mobile slurry. Using the dispersionmethod of the present disclosure (i.e. that involving an aromaticcarboxylic acid or aromatic sulphonic acid or derivatives thereof ascontrolling agent) the bulk density of the isolated polymer is muchhigher thus permitting the use of much lower volume work-up vessels andsignificantly reducing the amount of water required to purify theisolated polymer.

The ability to recover the solvent and the controlling agent and thereduction in the amount of water required in the process provides a moresustainable and cost-effective process than the prior art methods whichrequire solvent mixtures, controlling agents which are difficult toremove and large quantities of water.

Polymerising agents such as terephthaloyl chloride (TPC) andisophthaloyl chloride (IPC) may also be used. This is optional if aself-polymerising monomer is used.

A Lewis acid is used as catalyst. The term “Lewis acid” is used to referto a substance which can accept a shared electron pair from anothermolecule. Suitable catalysts for use in the method of the presentdisclosure include aluminium trichloride, aluminium tribromide, antimonypentachloride, antimony pentafluoride, indium trichloride, galliumtrichloride, boron trichloride, boron trifluoride, zinc chloride, ferricchloride, stannic chloride, titanium tetrachloride, and molybdenumpentachloride. Preferably the catalyst is substantially anhydrousaluminium trichloride.

The amount of Lewis acid catalyst used will vary depending on theparticular monomers and the reaction medium selected. Typically, theamount of Lewis acid required is calculated on the basis of one Lewisacid for each ketone unit, plus an amount equimolar to that of Lewisbase, or controlling agent, plus up to 20% excess. Larger excesses canbe used but offer no significant advantage.

Alternative catalyst systems for electrophilic processes include use oftrifluoromethanesulphonic acid, with and without P₂O₅, and those usingmixtures of CF₃—COOH and CF₃—SO₃H with and without P₂O₅. Terephthalicand isophthalic acids can be used in these super acid mixtures. Forexample, PEKK can be produced from EKKE plus terephthalic andisophthalic acids in CF₃—SO₃H, with the CF₃—SO₃H is used as the solvent.The CF₃—SO₃H reacts with the tere/iso acids to give the mixedcarboxylic-sulphonic anhydride CF₃—SO₂—O—CO-Ph-CO—O—SO₂—CF₃ which in thepresence of an electron rich —H group as in EKKE then eliminate CF₃—SO₃Hand forms a ketone unit. As an alternative to CF₃—SO₃H, CF₃—COOH withsome CF₃—SO₃H plus P₂O₅ to remove the water produced may be used.

If necessary, capping agents which do not contain an amine group(protected or otherwise) may be added to the polymerisation reactionmedium to cap the polymer on at least one end of the polymer chain. Thisterminates continued growth of that chain and controls the resultingmolecular weight of the polymer. Use of these capping agents maytherefore be used to produce polymers within a selected narrow molecularweight range. In this aspect, both nucleophilic and electrophiliccapping agents may be used to cap the polymer at each end of the chain.Such capping agents, if used, will be used in addition to the cappingagent which comprises —NR₂, —NRH or a protected amine, which is used toproduce the functionalised compounds of the present disclosure.Preferred nucleophilic capping agents of this type are 4-chlorobiphenyl,4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone, biphenyl4-benzenesulphonylphenyl phenyl ether, and the like. Typicalelectrophilic capping agents include benzoyl chloride, benzenesulfonylchloride and the like.

Preferred solvents for the electrophilic polymerisation reaction arehalogenated hydrocarbons (e.g. tetrachloroethylene,1,2,4-trichlorobenzene, o-difluorobenzene, 2-dichloroethanedichlorobenzene, 1,1,2,2,-tetrachloroethane, particularlyortho-dichlorobenzene, dichloromethane etc.). Additionally, oralternatively, non-chlorinated diluents may be used such as cyclohexane,carbon disulphide, nitromethane, nitrobenzene, HF. Dichloromethane (DCM)is particularly preferred for use in the present disclosure.

A non-protic diluent can also be employed, if desired. Advantageously,the diluent should be inert towards Friedel-Crafts reactions. Otherdiluents include, for example, dichloromethane, carbon disulphide,o-dichlorobenzene (i.e. ortho- or 1,2-dichlorobenzene),1,2,4-trichlorobenzene, o-difluorobenzene, 1,2-dichloroethane,cyclohexane, 1,1,2,2,-tetrachloroethane and mixtures thereof. Whilstthese additional diluents may be used they confer no significantadvantage to the process and may result in difficulty in separating thediluents used for further use. A process which is substantially freefrom co-solvent is therefore a preferred aspect of the presentdisclosure.

The amount of any diluent used is most preferably in the range of 10 mLto 400 mL, especially 50 mL to 200 mL of diluent to 10 g of polymer.Both higher and lower concentrations (preferably higher) may be used ifrequired.

When electrophilic polymerisation is complete, the polymer containsLewis acid catalyst complexed to any carbonyl groups (and possibly alsoto ether groups). The catalyst residue must be removed, i.e. the Lewisacid must be decomplexed from the polymer and removed. Decomplexationcan be accomplished by treating the polymerization reaction mixture witha decomplexing base after completion of polymerization. The decomplexingbase must be at least as basic towards the Lewis acid as the basicgroups on the polymer chain.

The amount of decomplexing base used should be in excess of the totalamount of bound (complexed) and unbound Lewis acid present in thereaction mixture and is preferably at least twice the total amount ofLewis acid. Typical decomplexing bases which can be used include water,dilute aqueous hydrochloric acid, methanol, ethanol, acetone,N,N-dimethylformamide, N,N-dimethylacetamide, pyridine, dimethyl ether,diethyl ether, tetrahydrofuran, trimethylamine, trimethylaminehydrochloride, dimethyl sulphide, tetramethylene sulphone, benzophenone,tetramethylammonium chloride, isopropanol, acetic acid and the like.Iced water or cooled dilute hydrochloric acid are preferred for use inthe present disclosure.

The electrophilic process can be carried out in a manner similar tostandard suspension polymerisation reactions. The reactions aregenerally carried out in a dry and/or inert, preferably dry, especiallydry and inert atmosphere, e.g. reaction vessels may be purged with dryair, nitrogen, argon or CO₂. Typically, the catalyst (e.g. AlCl₃) isadded to the cooled solvent (preferably dichloromethane, preferablycooled to well below room temperature, e.g. −20° C.) followed by thecontrolling agent (preferably benzoic acid) followed by the monomers andend-capper. Further monomer or monomer mixtures, if required, may thenbe added in a solution of the same solvent or as solids. The controllingagent may be added earlier or later in the sequence of additions,preferably after the catalyst and before the monomers, provided thetemperature of the slurry is kept below −10° C. during the addition,preferably below −20° C. Additional reaction components, e.g. cappingagents, additional diluent etc., are typically also added at this stage.The capping agent can be added later, even after the mixture has warmed.This has the effect of altering the molecular weight distribution whichcan be advantageous in some instances.

When a copolymer is to be produced, the monomer system suitable forforming aryletherketone units is polymerised before, after, or at thesame time as, the comonomer. For the formation of random copolymers, alltypes of monomer may be added and/or polymerised together. For theformation of block copolymers, at least one type of monomer is addedafter at least one other has polymerised, e.g. the monomer systemsuitable for forming aryletherketone units is polymerised before orafter the comonomer.

The resulting reaction mass is then typically allowed to warm towardsroom temperature while being stirred vigorously in a suitably baffledreactor. During the polymerisation, any by-products (e.g. condensationproducts) (e.g. hydrogen chloride) can be trapped and disposed of. Afterstirring at room temperature for a suitable length of time (in general 4to 8 hours, preferably 6 hours) work-up/decomplexation can begin bycombining the entire reaction mass with decomplexing base (e.g. icedwater). Care must be taken to avoid the temperature of the decomplexingmixture rising above room temperature (+25° C.). Prior to decomplexationthe reaction mass is typically an orange slurry and after completedecomplexation the mass is usually a snow white/off white slurry. Themass is then typically stirred at or below room temperature to yield thefinal polymer product.

Solvent removal from this product may be carried out by any conventionalmethod, although typically this will be by distillation. Furtherpurification can be achieved by known methods, e.g. hot filtration ofthe suspension to yield the polymer product, typically as a snowwhite/off white residue. Cooling of the combined filtrates, includingany acidic washes (e.g. to 5° C.) results in recovery of any benzoicacid used as the controlling agent by crystallisation. Using thesemethods, up to 95% of the solvent, usually dichloromethane, can berecovered along with up to 90% of the controlling agent (e.g. when thecontrolling agent is benzoic acid or a benzoic acid derivative).

The polymers produced by way of the methods herein described areconsidered to form a further aspect of the present disclosure.

Thus, in a further aspect, the present disclosure provides anamine-functionalised (e.g. amine-terminated) polyaryletherketonepolymer, or imide- or sulphone-copolymer thereof, obtainable by anyprocess as herein described (preferably in particulate form).

In one aspect, the present disclosure provides particles of anamine-functionalised (e.g. amine-terminated) polyaryletherketonepolymer, or imide- or sulphone-copolymer thereof and amine-protectedanalogues thereof, obtained or obtainable by a method comprising thestep of polymerising a monomer system in a reaction medium comprising:

-   -   (i) a capping agent comprising —NR₂, —NRH or a protected amine        group,    -   (ii) a Lewis acid and    -   (iii) and a controlling agent comprising an aromatic carboxylic        acid, an aromatic sulphonic acid, or a derivative thereof.

A further advantage of the present disclosure is that the process, whencarried out with the carboxylic acid or sulphonic acid based controllingagent herein described, can yield polymer particles, i.e. the polymer inparticulate form, e.g. spheres of functionalised polyaryletherketonesand imide or sulphone-copolymers thereof, e.g. PEKK. The provision ofspherical particles directly from the polymer production process isparticularly advantageous as it means that costly further processingsteps such as grinding and sieving are not necessary. Instead, theprocess gives spherical particles directly. Moreover, the sphericalparticles produced according to the present disclosure are more uniformin shape rather than the rough particulates that would be produced bygrinding.

Particles of functionalised polyaryletherketones have, until now, beenunobtainable, and thus form a preferred aspect of the presentdisclosure. Therefore, the present disclosure provides particles, e.g.spherical or substantially spherical particles of theamine-functionalised polymers of the present disclosure.

For processes that do not directly result in particles, the resultingpolymer materials can be ground to particles if required.

The particle shape may be irregular, e.g. lozenge shaped, fibrous or rodshaped, preferably with an aspect ratio 1.5 to 10 (where R=a/b, “a” isthe largest dimension, and “b” is the smallest dimension), however, inpreferred embodiments the polymer particles are primarily, i.e.substantially, spherical, preferably substantially spherical in shapewith an aspect ratio (R) of about 1 to 1.5. The polymer morphology is ina semi-crystalline state with the degree of crystallinity greater than5% to impart good chemical resistance and low moisture pick-up. Theparticles' physical structure may range from being solid (high density;e.g. density of 1.3 g/cc or greater) to cellular (density of <1 g/cc)structure, or a combination of the two.

By “particle size” is meant particle diameter. The particles accordingto the present disclosure advantageously have particle sizes (e.g. asmeasured with a Malvern Mastersizer particle size analyser) of 0.1 to3000 μm, preferably 1 to 500 μm, especially preferably 1 to 100 μm,particularly 10 to 200 μm, e.g. 50 to 100 μm. Preferably the particleshave one dimension that is 75 μm or less, e.g. 10 to 50 μm. Especiallypreferably, the particles are substantially spherical particles havingdiameter of less than 75 μm.

Preferably, the particles are substantially spherical in shape with anaspect ratio (R) of about 1 to 1.5.

Typically, at least 25% (by volume) of the particles are less than 100μm in diameter, preferably at least 50%, e.g. at least 75%.Alternatively, or additionally, at least 20% of the particles are lessthan 70 μm, preferably at least 40%, e.g. at least 60%.

The particles preferably have a coefficient of variation (CV) of lessthan 20%, e.g. less than 10%, more preferably less than 5%, still morepreferably less than 2%. CV is determined in percentage as,CV=100×standard deviation mean where mean is the mean particle diameterand standard deviation is the standard deviation in particle size. CV ispreferably calculated on the main mode, i. e. by fitting a monomodaldistribution curve to the detected particle size distribution. Thus someparticles below or above mode size may be discounted in the calculationwhich may for example be based on about 90% of total particle number (ofdetectable particles that is). Such a determination of CV is performableon a Malvern Mastersizer particle size analyser.

Preferably the polymers or copolymers of the present disclosure have aweight average molecular weight (Mw) of at least 8,000, preferablygreater than 9,000, especially greater than 10,000, more specifically,in the range of 8,000-162,000, more preferably, 26,000-162,000. TheM_(w) as disclosed herein can be determined by gel permeationchromatography (GPC).

Preferably the polymers or copolymers of the present disclosure have aninherent viscosity (IV) of at least 0.2 dl/g, e.g. at least 0.28 dl/g,especially at least 0.4 dl/g, particularly preferably at least 0.5 dl/g.Preferred ranges are 0.4-1.7 dl/g, e.g. 0.6-1.5 dl/g. IV as discussedherein can be measured by using a conventional viscometer.

Preferably the polymers or copolymers of the present disclosure have aglass transition temperature (T_(g)) of at least 140° C. as measured bydifferential scanning calorimetry (DSC), more specifically, in the rangeof 140-178, especially at least 144° C., particularly preferably atleast 148° C., e.g. 158-178° C.

The size of the polymer particles may be controlled by varying theamount of dispersant added, amount of polymer per unit volume ofsolvent, the stirrer speed, the stirrer paddle design, temperature ramprate, the reactor design and/or the addition of baffles to createturbulence. Other techniques well known in dispersion polymer chemistrymay be employed. However, the present inventor has surprisingly foundthat, not only can the present disclosure provide spherical particles ofPAEKs for the first time, but the method allows the particle size (e.g.distribution and/or mean) to be controlled by varying the amount ofcontrolling agent (preferably benzoic acid) used.

It has been found that increasing the amount of carboxylic/sulphonicacid based controlling agent relative to the amount of monomers resultsin the average particle size decreasing. Typical ranges of ratio ofmoles of controlling agent to moles of acid halide groups present in themonomer system are described herein.

The actual amount of controlling agent added depends upon, inter alia,the particular controlling agent used, the nature of the monomerspresent and the type and amount of Lewis acid employed. As noted above,the ranges given particularly apply to the controlling agents containingone carboxylic acid or sulphonic acid functionality, e.g., those listedas (i) to (iv) above where y or z is equal to 1. For those controllingagents containing more than one acid group per molecule, e.g. where y orz is not 1, the equivalents of controlling agent to acid halide groupsin the monomer systems may be adjusted accordingly.

The higher relative amounts of controlling agent can produce particlesof a smaller mode particle size than the lower amounts of controllingagent. It has been found that controlling the particle size isparticularly suited to PAEKs in which the 1,4-linked units are presentin 50% or more by weight.

As well as decreasing the size of the particles produced, increasing therelative amount of controlling agent used can result in extremely smallparticles being formed. For example, particles of less than one micron,i.e. as small as 0.275 μm have been recorded. If very small particlesare desired, the amount of controlling agent (and/or other factors knownto influence particle size in polymerisation reactions) can be chosen tooptimise the amount of smaller particles and the smallest particlesremoved from the product mixture, e.g. by using conventional techniquessuch as sieving, air classification (e.g. air elutration),photoanalysis, optical counting methods, electroresistance countingmethods, sedimentation techniques, laser diffraction methods, acousticspectroscopy, ultrasound attenuation spectroscopy etc.

By varying the amount of controlling agent and separating the particlesbased on their size, the present disclosure allows PAEKs of gradedparticle sizes to be produced. This lends the polymer to a variety ofdifferent applications as the size range of the particles can becontrolled to suit the end use. For example, very small (e.g. sub-micronparticles) could be used for powder impregnation of composites.

Thus the present disclosure provides a method for producing an aminefunctionalised polyaryletherketone as herein described, having aselected particle size distribution, said method comprising thefollowing steps:

(i) polymerising a monomer system in a reaction medium comprising:

-   -   (a) a Lewis acid;    -   (b) a controlling agent comprising an aromatic carboxylic acid,        an aromatic sulphonic acid, or a derivative thereof; and    -   (c) a capping agent comprising —NR₂, —NRH or a protected amine        functional group and        (ii) adjusting the ratio of controlling agent to monomers in the        monomer system whereby to control particle size distribution.

Preferably, the particle size is selected by adjusting the ratio ofmoles of carboxylic/sulphonic acid type controlling agent to moles ofacid halide groups present in the monomer system. Typical ratios ofmoles of controlling agent to moles of acid halide groups present in themonomer system are from 0.1 to 10, preferably 0.5 to 7, especially 0.7to 5, particularly preferably 1.5 to 2.

Viewed from a further aspect, the present disclosure providesamine-functionalised (e.g. amine-terminated) polyaryletherketone-imidecopolymers or polyaryletherketone-sulphone copolymers, andamine-protected analogues thereof.

The above-mentioned polymers and spherical particles of polymer form afurther aspect of the present disclosure, as do their uses andarticles/composites comprising them. The present disclosure thusprovides particles, e.g. substantially spherical particles, ofamine-functionalised (e.g. amine-terminated) polyaryletherketonepolymer, or imide- or sulphone-copolymer thereof, as herein described.

Compositions comprising functionalised PAEKs as herein described,especially spherical particles of amine-functionalised PAEKs may containor comprise the particles (e.g. spherical particles) ofamine-functionalised PAEKs in a suitable matrix, for example anotherpolymer, such as a thermoplastic or thermoset. The particles can also beutilised as the powders in powder impregnated fibre composites.

The polymer particles may be solid, hollow or porous, e.g. porous withan outer shell. In the case where porous or hollow particles are formed,these may be used to encapsulate or support materials, e.g. activeagents in order to impart extra functionality to the polymer. Forexample, the cellular structure of particles of the present disclosurecan allow penetration of liquid thermoset resin to infuse and react toform an interpenetrating network at the article surface

The functional groups of the materials of the present disclosure may beused to attach the polymer (e.g. polymer particles) covalently to othermaterials, e.g. other polymers and can be used, for example, in theproduction of toughened polymer materials.

The polymers of the present disclosure may be blended with otherpolymers in order to produce polymer blends suited to a variety ofpurposes. Moreover, articles comprising the polymers of the presentdisclosure form a further aspect of the present disclosure.

The present disclosure will now be further described by the followingnon-limiting examples and figures.

FIG. 1 shows the produced functionalized PEKK particles with differenttere:iso (T:I) ratios, produced according to Examples 1 (100:0), 2(80:20) and 4 (60:40).

FIG. 2 shows co-polymer backbone PEKK imide and cross-linked versionsproduced according to Examples 9 and 5 at different magnificationsshowing size, shape, and surface features

FIGS. 3 and 4 are scanning electron micrograph (SEM) images of aminereactive end cap PEKK polymer particles produced according to Example 2with T:I ratio of 80:20 at 500× and 2000× magnification, respectively.These images show spherical particles that are on average 50-60 μm indiameter with some agglomeration of the particles as shown in FIG. 3.The surface features of the spherical particle as shown in FIG. 4 havecharacteristics similar to a “raisin” that the crevices and ridges wereformed possibly due to contraction of the particle upon precipitatingfrom solution.

Table 1 shows the key information for the unfunctionalised (i.e. withoutamine end caps, prepared according to the method of WO 2011/004164) andamine end cap functionalized PEKK particles obtained according to thepresent invention. The inherent viscosities of both polymers weresimilar indicating similar molecular weights. The functionalized PEKKparticle used the trifluoroacetyl protection route which was removed bytreating the particles with a strong base to remove the trifluoroacetylprotecting group to obtain the reactive amine end group.

TABLE 1 Inherent Viscosity Particle ID (dl/g) Capping agentUnfunctionalised 0.31 None Functionalized 0.28 CF₃-EC

EXAMPLE 1: METHOD FOR THE PRODUCTION OF ALL 1,4-(100:0) PEKK WITHTERMINAL NH₂ FUNCTIONALITY, 5% OUT OF BALANCE

The reaction vessel was a glass, round bottomed, jacketed five litrereaction vessel with a bottom outlet and four baffles. Dichloromethane(2500 ml) was placed in the reaction vessel which was fitted with anoverhead stirrer with an anchor head plus two intermediate paddles setat 90°, a solids inlet, a nitrogen inlet and a thermocouple. Thetemperature of the vessel was controlled by a Julabo externalcooler/heater unit and was logged using Julabo EasyTemp software.

The vessel was purged with nitrogen and the dichloromethane cooled to−20° C. with stirring at 200 rpm, this stirring rate was used throughoutthe addition of all the reactants. The nitrogen purge was removed duringthe solid additions but reconnected during longer cooling periods.Aluminium chloride (AlCl₃) (764.8 g, 5.74M) was added to the cooleddichloromethane resulting in a small temperature increase. On coolingback to −20° C., benzoic acid (292.96 g; 2.399M) was added slowly to theAlCl₃ slurry such as to maintain the temperature of the slurry bellow−10° C. The dichloromethane slurry developed a yellow colour due to thealuminium chloride; the majority of it remained at the bottom of thevessel. The reaction mixture was then allowed to cool back to −20° C.

Maintaining the reaction mixture below −5° C.1,4-bis(4-phenoxybenzoyl)benzene (EKKE) 265.99 g; 0.5653M) was carefullyadded in portions. At this point the mixture turned bright opaqueorange. The remaining monomer was transferred by washing withapproximately 4×50 ml (200 ml) portions of dichloromethane.Terephthaloyl chloride (TPC) (120.81 g; 0.5951 M) was carefully added ata rate so as not to allow the mixture to rise above −10° C. Theterephthaloyl chloride residues were transferred into the vessel bywashing with approximately 200 ml dichloromethane in three portions.

Lastly the end-capper (“CF₃-EC”), 2,2,2-Trifluoro-N-(4-phenoxyphenyl)acetamide (16.69 g, 0.0596M) obtainable from Chem Bridge Corporation,San Diego, USA and purified prior to use was added with its washings,together with the remaining 100 ml of dichloromethane. The stirrer speedwas increased to 500 rpm and maintained over the reaction time. Thereaction mixture was slowly warmed to 5° C. then after 10 minutes to 20°C., where it was kept constant throughout the reaction time. Afterapproximately 30 minutes all of the solids had dissolved forming anorange-red solution. After this point, dispersed polymer particles beganto form. The reaction mixture was stirred rapidly for five hours.Sometimes it is necessary to add an additional 500 ml of dichloromethaneto replace material that evaporates during the reaction. If the reactionis carried out in a pressurised vessel this will not be necessary.During this phase the nitrogen purge was replaced with a trap to collectand neutralise the hydrogen chloride evolved during the reaction.

The reaction mixture was removed from the vessel via the bottom outlet.

The reaction mixture is removed from the reaction vessel and isolated byvacuum filtration through a sinter. The orange solid was transferred toand decomplexed in approximately three litres of iced deionised waterwith stirring to produce a white particulate product. Duringdecomplexing, the mixture should not reach greater than 5° C. Thefiltrate is also poured into iced water for decomplexing and disposal.The polymer remains in deionised water until workup. Prior to workup,the polymer particles should be entirely white, with no orange residues.

Workup procedures are typically carried out using a stirrer hotplate.Constant stirring is achieved with a large magnetic stirrer bar. Arepresentative workup procedure for a PEKK polymerisation carried out ina one litre reactor is as follows:

-   -   Stand/stir in deionised water overnight at room temperature.    -   Filtered and slowly added to 1.5 litres of stirred, hot        deionised water to remove the residual dichloromethane    -   100 ml concentrated hydrochloric acid added, boiled for 1 hour,        filtered, washed with 500 ml deionised water, filtered    -   Slurry in 2 litres of deionised water, boiled for 1 hour,        filtered, washed with 500 ml deionised water, filtered Repeat        the above.    -   Slurry in 2 litres of deionised water made to pH13 with ammonia        solution (˜30 ml), boiled for 1 hour, filtered, washed with 500        ml deionised water, filtered    -   Slurry in 2 litres deionised water, boiled for 1 hour, filtered,        washed with 500 ml deionised water, filtered    -   Pale cream PEKK powder isolated

During this process the trifluoroactetyl protecting groups are removedfrom the end-capper leaving free terminal amine functionality.

The powder was first dried at 120° C. overnight, or until dry, in an airoven. The powder was then re-dried at 200° C. overnight in a vacuum ovenwhere the oven was continuously evacuated.

Dry yield ˜270 g: 80% yield. The process produces a reasonable quantityof very fine particles and much of this is lost during the filtrationsteps.

The IV of the resultant polymer was 0.85 dl/g. T_(g) 182° C.; T_(m) 396°C. The presence of the primary amine group was confirmed by using theNihydrin test and the Infra-Red spectrum of FIG. 5.

EXAMPLE 1A: COMPARISON OF IV VALUES FOR FUNCTIONALISED ANDUNFUNCTIONALISED POLYMERS

As in Table 1 above, the IV value for the polymer of Example 1 (0.85dl/g) was found to be comparable to that found for an unfunctionalised(i.e. non-amine terminated) analogue, the latter being capped using abenzoyl group and having an IV value of 0.91 dl/g. The unfunctionalisedpolymer was prepared according to a method similar to that of Example 2of WO 2011/004164 (this method being 3.5% out of balance whereas Example2 of WO 2011/004164 was 2.24% out of balance).

The reagents used to produce the unfunctionalised PEKK were:

1,4-bis(4-phenoxybenzoyl)benzene—0.1063M-50 g

terephthaloyl chloride—0.08204M-16.655 g

isophthaloyl chloride—0.02051 M-4.163 g

Benzoic acid—0.41 M-50 g

Aluminium trichloride—1.002M-133.64 g

Benzoyl chloride—0.003754M-0.5277 g

Dichloromethane 450 ml

To a 700 ml reaction flask equipped with a mechanical stirrer, havingbeen purged with dry nitrogen, was added the1,4-bis(4-phenoxybenzoyl)benzene along with 300 ml of dichloromethane.Having cooled the slurry to −20° C., the anhydrous aluminium trichloridewas slowly added so as not to raise the temperature of the slurry above−10° C. and to minimise any splashing up the walls of the reactor. Aftercooling back to −20° C., a mixture of isophthaloyl chloride andterephthaloyl chloride was added to the slurry along with a further 100ml of dichloromethane. Also at −20° C., the benzoic acid was added,followed by the benzoyl chloride as a capping agent.

Whilst stirring at 100 rpm the reaction mass was allowed to warm towardsroom temperature without additional heating. During this period, thecolour of the reaction mass changed from yellow to pale orange. As themass showed signs of phase separating, the speed of the stirrer wasraised to 350 rpm and this speed was maintained for the duration of thesynthesis. During the polymerisation, hydrogen chloride was evolvedwhich was trapped and disposed of safely.

After stirring at room temperature for 6 hours the reaction mass waspoured into 5 litres of iced water (care must be taken to avoid thetemperature of the decomplexing mixture rising above room temperature).The aqueous mass was then stirred at room temperature for 4 hours oruntil all of the orange colouration had disappeared leaving a snow whitemass.

Having transferred the white mass to a suitable vessel, the vessel washeated and the dichloromethane distilled off. Having removed all of thedichloromethane, the mass was brought to reflux and refluxed for 1 hourwhereupon the suspension was filtered whilst hot. While the filtrate wasleft to cool the white polymer solid was added to a further 3 litres ofdeionised water and brought to reflux. This was repeated a further twotimes and in each case the filtrate was added to the initial filtrateand allowed to cool. The polymer powder was then dried overnight at 150°C. under a partial vacuum. On cooling, benzoic acid crystallised fromthe combined filtrates. The yield of benzoic acid was enhanced bychilling the filtrates to 5° C.

EXAMPLE 2: METHOD FOR THE PRODUCTION OF 1,4:1,3—(80:20) PEKK WITHTERMINAL NH₂ FUNCTIONALITY, 5% OUT OF BALANCE

This was carried out in exactly the same manner as example 1 but wherethe quantities of terephthaloyl (TPC) and Isophthaloyl (IPC) chlorideswere 73.69 g, 0.3630M and 47.12 g 0.2321M respectively.

The IV of the resultant polymer was 0.81 dl/g. T_(g) 165° C.; T_(m) 355°C.

EXAMPLE 3: METHOD FOR THE PRODUCTION OF 1,4; 1,3-(70:30) PEKK WITHTERMINAL NH₂ FUNCTIONALITY, 5% OUT OF BALANCE

This was carried out in exactly the same manner as example 1 but wherethe quantities of TPC and IPC chlorides were 50.13 g, 0.2470M and 70.68g 0.3481M respectively.

IV of the resultant polymer was 0.79 dl/g. T_(g) 160° C., T_(m) 338° C.

EXAMPLE 4: METHOD FOR THE PRODUCTION OF 1,4; 1,3—(60:40) PEKK WITHTERMINAL NH₂ FUNCTIONALITY 5% OUT OF BALANCE

This was carried out in exactly the same manner as example 1 but wherethe quantities of TPC and IPC chlorides were 26.58 g, 0.1309M and 94.23g 0.4642M respectively.

The IV of the resultant polymer was 0.83 dl/g. T_(g) 158° C.

EXAMPLE 5: METHOD FOR THE PRODUCTION OF 1,4; 1,3—(80:20) PEKK WITHTERMINAL NH₂ FUNCTIONALITY 5% CROSSLINKED, 5% OUT OF BALANCE

This was carried out using the procedure in example 1 using thefollowing reagents:

EKKE 267.88 g (0.5693M) TPC  68.39 g (0.3369M) IPC  45.67 g (0.2249M)1,3,5 Benzenetricarbonyl chloride  5.25 g (0.025M) Benzoic acid 289.16 g(2.37M) Aluminium trichloride 750.43 g (5.63M) CF₃-EC  16.84 g (0.0599M)

Note: This is on the basis of end group concentration.

Total acid chloride end group conc. is (0.3369+0.2249)×2+0.025×3=1.1986

5% Out of balance is 0.95×1.1986=1.1387 or 0.5693M of EKKE=267.88 g

Required CF₃-EC is 1.1986-1.1387=0.0599M=16.85 g

The IV of the resultant polymer was 1.5 dl/g. T_(g) 166° C.; T_(m) 352°C.

EXAMPLE 6: METHOD FOR THE PRODUCTION OF A PEKK-IMIDE (70:30), ALLTEREPHTHALOYL WITH TERMINAL NH₂ FUNCTIONALITY 5% OUT OF BALANCE

This was carried out using the procedure in example 1 where some of theEKKE is replaced by the bis-imide monomer5,5′-Oxybis(2-(4-phenoxyphenyl)isoindoline-1,3-dione) “EIEIE”.

EKKE 139.64 g, (0.2968) EIEIE  81.99 g, (0.1272M) TPC  90.62 g,(0.4463M) Benzoic acid   218 g, (1.785M) Aluminium trichloride 612.38 g,(4.593M) CF₃-EC  12.54 g, (0.0446M)

The IV of the resultant polymer was 0.78 dl/g. T_(g) 178° C.; T_(m) 342°C.

EXAMPLE 7: METHOD FOR THE PRODUCTION OF NH₂ END-CAPPED 80:20 PEKK; 5%OUT OF BALANCE

The reaction vessel was a glass, round bottomed, jacketed two litrereaction vessel. Dichloromethane was placed in the reaction vesselfitted with an overhead stirrer with an anchor head, a solids inlet, anitrogen inlet and a thermometer.

Dichloromethane (500 mL) was added to the vessel which was purged withdry nitrogen cooled to −20° C. with stirring at 200 rpm. The mixture inthe reaction vessel was stirred constantly at a rate of approximately200 rpm during the following additions. The nitrogen purge was removedduring the additions but reconnected during longer cooling periods.Aluminium chloride (80.56 g, 0.6042M) was added, followed by dimethylsulphone (15.25 g, 0.162M), not allowing the mixture to rise above −10°C. due to the exotherms. The dichloromethane developed a yellow colourdue to the aluminium chloride, the majority of it remained at the bottomof the vessel. The reaction mixture was then allowed to cool back to−20° C.

A mixture of terephthaloyl chloride (9.6657 g; 0.0476M) and isophthaloylchloride (6.7305 g; 0.03315M) was carefully added at a rate so as not toallow the mixture to rise above −10° C. The remaining acid chlorideswere transferred by washing with approximately 50 ml dichloromethane inthree portions. 1,4-Bis(4-phenoxybenzoylbenzene) (40 g; 0.085M) wascarefully added at a rate so as not to allow the mixture to rise above−5° C. At this point the mixture turned bright opaque orange. Theremaining monomer was transferred by washing with approximately 50 mldichloromethane in three portions.

Lastly, (CF₃-EC) 2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide (2.3849 g;0.00848M) was added with its washings (50 ml) of dichloromethane. Thestirrer speed was maintained at 200 rpm and maintained over the reactiontime. The reaction mixture was slowly warmed to 5° C. then after 10minutes to 20° C., where it was kept constant throughout the reactiontime. Upon warming, the nitrogen purge was removed and evolved hydrogenchloride captured using an aqueous solution of sodium bicarbonate. Afterapproximately 30 minutes all of the solids had dissolved forming anorange-red solution. After this point the reaction mixture phaseseparated and eventually formed a gel. After full gellation the stirrerwas stopped and the mixture maintained at +20° C. for between 4 and 5hours. At the end of the reaction time the gel was removed from thevessel. The polymer complex was decomplexed in iced water using a 4 LWaring blender giving a snow white solid. When fully decomplexed thepolymer was filtered off and washed with 1.5 L of deionised water. Thepolymer fluff was re-slurried in 2 L of deionised water and leftstirring overnight under a flow of filtered air to remove most of thedichloromethane.

Prior to workup, the polymer particles should be entirely white, with noorange parts remaining.

Work up procedure:

-   -   Stand in deionised water overnight    -   Filtered and slowly added to 1.5 litres of stirred, hot        deionised water to remove the residual dichloromethane    -   100 ml concentrated hydrochloric acid added, boiled for 1 hour,        filtered, washed with 500 ml deionised water, filtered    -   1.5 litres of deionised water, boiled for 1 hour, filtered,        washed with 500 ml deionised water, filtered    -   1.5 litres deionised water, boiled for 1 hour, filtered, washed        with 500 ml deionised water, filtered    -   1.5 litres deionised water made to pH 13 with ammonia solution        (˜30 ml), boiled for 1 hour, filtered, washed with 500 ml        deionised water, filtered    -   1.5 litres deionised water, boiled for 1 hour, filtered, washed        with 500 ml deionised water, filtered    -   Off-white PEKK powder isolated

The polymer was dried overnight under vacuum at 125° C. followed byfurther drying at 200° C. under vacuum also overnight.

The resulting polymer had an IV of 0.6 dl/g. The polymer structure andthe presence of free (unprotected) secondary amine groups were confirmedby ¹H, ¹³C NMR and FT-IR spectroscopy. The secondary amine groups werealso indicated using ninhydrin. DSC studies showed the polymer to have aT_(g) at 160° C. and T_(m) between 355-362° C.

Other examples at 3%, 4% and 7% out of balance were similarly preparedand characterised, together with examples where the terephthaloyl toisophthaloyl ratios were 100:0, 90:10, 70:30 and 60:40.

Similar results were obtained using N-acetyl-4-phenoxyaniline in placeof 2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide (CF₃-EC). However thework-up times needed to be extended to ensure complete removal of theless reactive protecting group.

EXAMPLE 8—SYNTHESIS OF AMINE TERMINATED 70:30 PEKKH₂N-PH-O-PH-[-CO-PH-CO-PH-O-PH-]_(N)-NH₂

A 2 L jacketed reaction vessel fitted with an efficient stirrer,thermometer, nitrogen inlet and gas outlet, containing 1 L of anhydrousdichloromethane was cooled to −20° C. under a nitrogen purge. To thecold stirred dichloromethane was added 113.6 gg (0.852 moles) ofanhydrous aluminium trichloride. During this addition the temperature ofthe dichloromethane rose to −12° C. After re-cooling to −15° C., 20.19 g(0.2145 moles) of dimethyl sulphone was slowly added to the slurrykeeping the temperature of the slurry below −5° C. At -10° C., 9.65 g(0.0475 moles) of Isophthaloyl chloride and 6.0779 g (0.0299 moles) ofterephthaloyl chloride were added to the reaction mixture. Care wastaken to ensure that both acid chloride residues were from the beakersand that caught on the addition funnel were completely washed into thereaction vessel using 100 cc of fresh dichloromethane. The temperaturerise during this addition was minimal. Again at −15° C., 38.3686 g(0.0816 moles) of 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) was slowlyadded to the slurry while maintaining the reaction temperature below−10° C. Residual EKKE was carefully washed into the reaction vesselusing 100 cc of fresh dichloromethane. After connecting the reactionvessel to an acid gas scrubber, the temperature of the reaction mixturewas increased to +20° C. over 45 minutes. Finally the protectedend-capper N-acetyl-4-phenoxyaniline 1.9316 g (0.00851 moles) was addedto the reaction mixture and any residues washed into the reaction vesselwith 50 cc of fresh dichloromethane. During this time all of thereaction solids dissolved to give a clear orange solution and hydrogenchloride was seen to be evolved. The temperature of the reaction vesselwas maintained at +20° C. for 6 hours. During the first 1.5 hours theviscosity of the orange solution increased until a gel was formedstopping the stirrer. At this point the stirrer was switched off.

The polymer complex was decomplexed by blending the orange rubbery massin a Waring blender in the presence of ice and water, the blendingmixture being kept below +20° C. During this process the polymer turnedfrom orange to show white. The white polymer fluff was filtered andwashed on the filter with 2×1 L of deionised water. After removing themajority of the water by vacuum filtration, the polymer was slurriedovernight in 4 L of deionised water at room temperature. Afterfiltering, the fluff was slowly added to 3 L of hot (70° C.) deionisedwater in portions to minimise foaming as the dichloromethane wasremoved. To the hot slurry was then added 150 mL of concentratedhydrochloric acid and the slurry refluxed for 3 hours to ensure completeremoval of the dichloromethane and removal of the protecting group. Thefluff was then filtered again and the fluff washed on the filter with2×2 L of deionised water. This process was then repeated. After therepeat the fluff was further refluxed for 1 hour in 4 L of deionisedwater containing 100 mL of 0.88 ammonia. After filtering and washingwith 2×2 L of deionised water the fluff was finally again refluxed in 4L of deionised water, filtered and washed.

The polymer fluff was dried overnight (16 hours) at 100° C. followed bya further drying at 200° C. for 8 hours under vacuum.

Optionally the polymer can be end capped using trifluoroacetyl protectedend-capper CF₃-EC (2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide) inplace of N-acetyl-4-phenoxyaniline (CH₃—CO—NH-Ph-O-Ph).

The IV of the polymer was 0.85 dl/g measure as a 0.1% solution inconcentrated sulphuric acid. T_(g) 164° C., T_(m) 338° C.

EXAMPLE 9—METHOD FOR THE PRODUCTION OF NH₂ END CAPPED 100:0 PEKK-EIEIEKK10% RANDOM COPOLYMER

The reaction vessel was a glass, round bottomed, jacketed five litrereaction vessel with a bottom outlet and four baffles. Dichloromethane(DCM) was placed in the reaction vessel fitted with an overhead stirrerwith an anchor head and additional agitation vanes up the length of thestirrer shaft, a solids inlet, a nitrogen inlet and a thermocouple. Thetemperature of the vessel was controlled by a Julabo externalcooler/heater unit and was logged using Julabo EasyTemp software.

The vessel was purged with nitrogen and the dichloromethane (DCM)allowed to cool to −20° C. with stirring at 200 rpm. The mixture in thereaction vessel was stirred constantly at a medium rate of approximately200 rpm during the following additions. The nitrogen purge was removedduring the additions but reconnected during longer cooling periods.Aluminium chloride (609.64 g. 4.572M)) was added, followed by benzoicacid (218.24 g, 1.787M)), not allowing the mixture to rise above −10° C.due to the exotherms. The dichloromethane (DCM) developed a yellowcolour due to the aluminium chloride, the majority of it remained at thebottom of the vessel. The reaction mixture was then allowed to cool backto −20° C.

Terephthaloyl chloride (90.60 g) was carefully added at a rate so as notto allow the mixture to rise above −10° C. The remaining acid chloridewas transferred by washing with approximately 100 ml dichloromethane(DCM) in three portions. (EIEIE) (82.20 g) was carefully added at a rateso as not to allow the mixture to rise above −10° C., causing themixture to turn bright opaque orange. The remaining monomer wastransferred by washing with approximately 50 ml dichloromethane (DCM) inthree portions. EKKE (1,4-bis(4-phenoxybenzoylbenzene) (140.00 g,0.2975M) was carefully added at a rate so as not to allow the mixture torise above −5° C. The remaining monomer was transferred by washing withapproximately 50 ml dichloromethane (DCM) in three portions.

Lastly, CF₃-EC (2,2,2-Trifluoro-N-(4-phenoxyphenyl) acetamide)(11.96 g,0.0426M)) was added with its washings, together with the remainingdichloromethane (DCM). The stirrer speed was increased to 500 rpm andmaintained over the reaction time. The nitrogen purge was removed andreplaced with a water pump fitted with an air vent so as not to placethe reaction system under vacuum. This was to trap and remove thehydrogen chloride evolved from the polymerisation. The reaction mixturewas slowly warmed to 5° C. then after 10 minutes to 20° C., where it waskept constant throughout the reaction time. After approximately 30minutes all of the solids had dissolved forming an orange-red solution.After this point, dispersed polymer particles began to form. Thereaction mixture was stirred rapidly for five hours. The reactionmixture was removed from the vessel via the bottom outlet.

The reaction mixture is removed from the reaction vessel and isolated byvacuum filtration through a sinter. The orange solid is decomplexed inapproximately three litres of iced deionised water with stirring toproduce a white particulate product. During decomplexation, the mixtureshould not reach greater than 5° C. The filtrate is also poured intoiced water for decomplexation and disposal. The polymer remains indeionised water until workup. Prior to workup, the polymer particlesshould be entirely white, with no orange parts remaining.

A representative workup procedure for a PEKK polymerisation carried outin a one litre reactor is as follows:

-   -   Stand in deionised water overnight    -   Filtered and slowly added to 1.5 litres of stirred, hot        deionised water to remove the residual dichloromethane (DCM)    -   Made up to 5 L with hot deionised water, 100 ml concentrated        hydrochloric acid added, boiled for 1 hour, filtered, washed        with 1 L deionised water, filtered    -   5 litres deionised water made to pH 13 with sodium hydroxide        pellets, boiled for 1 hour, filtered, washed with 1 L deionised        water, filtered    -   5 litres of deionised water, boiled for 1 hour, filtered, washed        with 1 L deionised water, filtered    -   5 litres of deionised water, boiled for 1 hour, filtered, washed        with 1 L deionised water, filtered    -   5 litres of deionised water, boiled for 1 hour, filtered, washed        with 1 L deionised water, filtered    -   Off-white PEKK powder isolated

The IV of the resultant polymer was 0.75 dl/g.

EXAMPLE 10—PREPARATION OF CAPPING AGENT—N-(4-PHENOXYPHENYL)ACETAMIDE

4-Phenoxyaniline (20.4 g, 0.110 mol) was dissolved in glacial aceticacid (200 ml) with stirring. To the very dark brown solution was addeddecolourising charcoal (3 g) and the resulting suspension stirred for 15minutes. The suspension was filtered through a Soxhlet thimble into aconical flask. On drainage of the thimble, further glacial acetic acid(200 ml) was filtered into the conical flask via the thimble. Aftercooling the conical flask in an ice bath to 5° C., acetic anhydride(11.1 cm³, 0.109 mol) was added to the aniline solution. An exothermicreaction occurred, raising the temperature to 30° C. After stirring for30 minutes the solution was poured into water (1000 ml) and stirred for10 minutes. After collecting the product by filtration the crude productwas dried in an air over overnight at 80° C. The crude product waspurified by crystallisation from hot methylcyclohexane (300 ml) anddecolorised using activated charcoal. The pale pink product wascollected by filtration, washed with 50 ml of methanol and dried undervacuum at 80° C. overnight. The product N-(4-phenoxyphenyl)acetamide wasisolated as a pink crystalline solid (21.0 g, 85%); purity 99.99 mol %(DSC), m.p. 131.2° C. {lit. 130-131° C.}. Structure confirmed by FT-IR,¹H NMR, ¹³C NMR and mass spectrometry.

EXAMPLE 11—4-PHENOXYANILINE BY THE HYDROLYSIS OF CF₃-EC,2,2,2-TRIFLUORO-N-(4-PHENOXYPHENYL)ACETAMIDE

A portion of CF₃-EC (2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide),purified prior to use, (100 mg, 0.36 mmol), was placed in a beaker withdeionised water (25 ml) and IPA (25 ml), and made up to pH 13 with asingle sodium hydroxide pellet, which caused CF₃-EC(2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide) to dissolve. The mixturewas heated at 85° C. for 1.5 hours, during which time a white suspensionwas produced. The solid was isolated by filtration and, washed withdeionised water and dried in an air oven to yield 4-phenoxyaniline as awhite crystalline solid (47 mg, 71%), mp 85.1° C. {lit. 85-86° C.};purity 99.95 mol % (DSC).

Structure confirmed by FT-IR, ¹H NMR, ¹³C NMR and mass spectrometry.

Model Compounds—Linear EXAMPLE 12—SYNTHESIS OF MODEL COMPOUND 3

DCM (50 ml) was added to a conical flask with a magnetic stirrer, andcooled in ice to 5° C. Aluminium chloride (5.03 g, 37.7 mmol) was added,with stirring, together with the DCM washings. Between each of thesubsequent additions and washings, the mixture was cooled in ice tobelow room temperature with stirring. Next, CF₃-EC(2,2,2-trifluoro-N-(4-phenoxyphenyl) acetamide) (4.17 g, 14.8 mmol) wasadded, followed by TPC (1.51 g, 7.44 mmol), including the DCM washings(100 ml total). The mixture was stirred at room temperature for 1.5hours, during which time the orange-brown solution became yellow. Thereaction mixture was poured into stirring iced water, yielding a whiteprecipitate in the DCM layer. This mixture was heated on a hotplate toremove the DCM. The cream precipitate 3 was isolated by filtration, waswashed with deionised water (3×50 ml) and dried in an air oven. Thecream product was recrystallised in dimethylacetamide, washed withacetone and dried in an air oven, yielding 5 as a grey solid (4.72 g,92%); mp 325.0° C.; purity 98.85 mol % (DSC); Structure confirmed byFT-IR, ¹H NMR, ¹³C NMR and mass spectrometry.

EXAMPLE 13—SYNTHESIS OF MODEL COMPOUND 4

DCM (50 ml) was added to a conical flask with a magnetic stirrer andcooled in ice to 5° C. Aluminium chloride (4.84 g, 36.3 mmol) was added,with stirring, together with the DCM washings. Between each of thesubsequent additions and washings, the mixture was cooled in ice tobelow room temperature with stirring. Next, CF₃-EC(2,2,2-Trifluoro-N-(4-phenoxyphenyl) acetamide)(4.16 g, 14.8 mmol) wasadded, followed by TPC (1.51 g, 7.44 mmol), including the DCM washings(100 ml total). The mixture was stirred at room temperature for 1.5hours, during which time the orange-brown solution became bright orange.The reaction mixture was poured into stirring iced water, yielding awhite precipitate in the DCM layer. This mixture was heated on ahotplate to remove the DCM. The cream precipitate 4 was isolated byfiltration, was washed with deionised water (3×50 ml) and dried in anair oven. The cream product was recrystallised in dimethylacetamide,washed with acetone and dried in an air oven, yielding 4 as a grey solid(4.76 g, 92%); m.p. 231.0° C.; purity 97.42 mol % (DSC); Structureconfirmed by FT-IR, ¹H NMR, ¹³C NMR and mass spectrometry.

EXAMPLE 14—SYNTHESIS OF MODEL COMPOUND 5 BY THE DEPROTECTION OF 3

A portion of 3 (130 mg, 0.188 mmol), was placed in a beaker withdeionised water (25 ml) and propan-2-ol (25 ml), and made up to pH 13with a single sodium hydroxide pellet, which caused 3 to dissolve. Themixture was heated at 85° C. for 1.5 hours, during which time a creamsuspension was produced. The solid was isolated by filtration, washedwith deionised water and dried in an air oven to yield 5 as a beigecrystalline solid (76 mg, 85%); mp 199.5° C., purity 97.63 mol % (DSC).

Structure confirmed by FT-IR, ¹H NMR, ¹³C NMR and mass spectrometry.

EXAMPLE 15—SYNTHESIS OF MODEL COMPOUND 6 BY THE DEPROTECTION OF 4

A portion of 4 (113 mg, 0.164 mmol), was placed in a beaker withdeionised water (25 ml) and IPA (25 ml), and made up to pH 13 with asingle sodium hydroxide pellet, which caused 4 to dissolve. The mixturewas heated at 85° C. for 1.5 hours, during which time a white suspensionwas produced. The solid was isolated by filtration, washed withdeionised water and dried in an air oven to yield 6 as a whitecrystalline solid (62 mg, 80%); m.p. 165.2° C.; purity 98.74 mol %(DSC).

Structure confirmed by FT-IR, ¹H NMR, ¹³C NMR and mass spectrometry.

Model Compounds—Trifunctional EXAMPLE 16—SYNTHESIS OF MODEL COMPOUND 1

DCM (100 ml) was added to a conical flask with a magnetic stirrer andcooled in ice to 5° C. Aluminium chloride (5.11 g, 38.3 mmol) was added,with stirring, together with the DCM washings. Between each of thesubsequent additions and washings, the mixture was cooled in ice tobelow room temperature with stirring. Next, 1,3,5-benzenetricarbonylchloride (1.52 g, 5.73 mmol) was added, followed by2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide (6.00 g, 21.3 mmol),including the DCM washings (100 ml total). The addition of2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide caused the solution to turngreen. The mixture was stirred at room temperature for 1.5 hours. After5 minutes the solution became orange, then after a further 15 minutes adark viscous liquid formed at the bottom of the flask. The resultingorange solution and dark orange viscous solid was poured into icedwater, and was stirred at a moderate speed for 1 hour, resulting in asmall amount of a white precipitate in the aqueous layer and an orangeorganic layer. This mixture was heated on a hotplate to remove the DCM.A green sticky solid was isolated by decanting the aqueous layer. Thissolid was dissolved in acetone (100 ml) and decolourising charcoal added(˜1 g). After stirring for 10 minutes, the solution was filtered,yielding a pale brown solution. On evaporation of the acetone, a brownsticky solid remained. This solid was stirred in methanol (100 ml),causing the precipitation of a white solid. The solid was isolated byfiltration and dried in an air oven, yielding 1 as a pale grey solid(0.78 g, 32%); m.p. 172.3° C.; purity 97.82 mol % (DSC).

Structure confirmed by FT-IR, ¹H NMR, ¹³C NMR and mass spectrometry.

EXAMPLE 17—SYNTHESIS OF MODEL COMPOUND 2

A portion of 1 (153 mg, 0.153 mmol), was placed in a beaker withdeionised water (25 ml) and propan-2-ol (25 ml), and made up to pH 13with a single sodium hydroxide pellet, which caused 1 to dissolve. Themixture was heated at 85° C. for 1.5 hours, during which time a yellowsuspension was produced. The solid was isolated by filtration, washedwith deionised water and dried in an air oven to yield 2 as a paleyellow solid (0.0771 g, 71%); mp 167.4° C., purity 97.72 mol % (DSC).

Structure confirmed by FT-IR, ¹H NMR, ¹³C NMR and mass spectrometry. Theprotected amine had been deprotected.

EXAMPLE 18—SULPHONE COPOLYMER (RANDOM)

As in example 1 where the reagents used were:

Reaction run 3% out of balance to give a random copolymer.

4,4′-diphenoxybenzophenone (EKE) 22.7547 g (0.0621M)4,4′-diphenoxydiphenylsulphone (ESE) 24.9934 g (0.0621M) Terephthaloylchloride (TPC)    26 g (0.1281M) CF₃-EC  2.1936 g (7.8 × 10⁻³M) Dimethylsulphone (Lewis base)  23.17 g (0.2462M) Aluminium trichloride (Lewisacid) Dichloromethane (DOM)

The polymer gel was decomplexed in ice/water using a Waring blender. Thepolymer fluff was worked up as in example 1.

IV of the resultant polymer was 1.13 dl/g. T_(g) was 183° C., thepolymer was amorphous.

EXAMPLE 19—SUPHONE COPOLYMER (BLOCK)

As in example 18 but the resultant polymer was a block co-polymer.

In this instance the ESE was first reacted with 9.4556 g (0.04657M) ofTPC and after 1 hour at 20 C the remainder of the TPC plus the EKE wasadded followed by the CF₃-EC. The polymer gel was worked up as inexample 18.

The IV of the resultant polymer was 1.08 dl/g. The T_(g) of the productwas 180° C. and the T_(m) 362° C. The polymer was semi-crystalline.

1. A method of preparing an amine functionalized polyaryletherketonepolymer, an imide- or sulphone-copolymer thereof or an amine-protectedanalogues thereof, said method comprising: polymerizing a monomer systemin a reaction medium comprising a Lewis acid and a capping agentcomprising —NR₂, —NRH or a protected amine group.
 2. (canceled)
 3. Themethod of claim 1, wherein said reaction medium further comprises acontrolling agent.
 4. The method of claim 3, wherein said controllingagent comprises an aromatic carboxylic acid, an aromatic sulphonic acid,or a derivative thereof.
 5. The method of claim 3, wherein saidcontrolling agent comprises a Lewis base.
 6. The method of claim 1,wherein said monomer system comprises an imide and/or sulphone monomer.7. The method of claim 1, wherein said capping agent is an agentrepresented by formula (Z)_(a)—Ar—(X)_(b) wherein: each X isindependently selected from the group consisting of —O—Ar, —C(═O)Cl,—C(═O)—Ar—O—Ar and —O—Ar—[—C(═O)—Ar—O—Ar-]_(c-)H, wherein each Ar isindependently an aromatic group; c is an integer, is a protected aminegroup, a is 1 to 5, and b is 1 to
 5. 8. The method of claim 1, whereinsaid controlling agent is one or more of (i) Ar′(COOX)_(y); (ii)Ar′(SO₃X)_(y); (iii) (Ar′COO⁻)_(z)M^(z+); or (iv) (Ar′SO₃ ⁻)_(z)M^(z+)wherein Ar′ is an aromatic group compatible with the remainingcomponents of the reaction medium; each X independently is a hydrogenatom or an organic group (R); each y independently is 1, 2 or 3; each Mindependently is a metal ion, and each z independently is an integerequal to charge on the metal ion (M^(z+)).
 9. The method of claim 1,wherein said polyaryletherketone is a homopolymer or copolymer of one ormore of the following repeat units: —Ar—O—Ar—C(═O)——Ar—O—Ar—C(═O)—Ar—C(═O)— —Ar—O—Ar—O—Ar—C(═O)——Ar—O—Ar—O—Ar—C(═O)—Ar—C(═O)— —Ar—O—Ar—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)—wherein each Ar is independently an aromatic moiety.
 10. The method ofclaim 9, wherein each Ar is independently selected from the groupconsisting of substituted and unsubstituted mononuclear aromaticmoieties and substituted and unsubstituted polynuclear aromaticmoieties.
 11. The method of claim 9, wherein Ar is phenylene.
 12. Themethod of claim 1, wherein said polyaryletherketone is a homopolymer.13. The method of claim 1, wherein said polymer is PEKK or an imide orsulphone copolymer thereof.
 14. The method of claim 3, wherein the Lewisacid is added to the reaction medium prior to the controlling agent. 15.The method of claim 14, wherein the components are added to the reactionmedium in the following order: (i) the Lewis acid (ii) the controllingagent (iii) the monomers and the capping agent.
 16. The method of claim1, wherein the amine-functionalized polyaryletherketone polymer is anamine-terminated polyaryletherketone polymer.
 17. The method of claim 7,wherein each Z is independently selected from the group consisting of—NHL, —NRL and —NL₂, each L is a leaving group independently selectedfrom the group consisting of an acetyl, haloacetyl, sulphonyl,halosulphonyl, —SO₂—R, c is 1 to 10, each R is independently analiphatic or aromatic group.
 18. The method of claim 7, wherein a is 1,2 or
 3. 19. The method of claim 7, wherein b is 1, 2 or
 3. 20. Themethod of claim 17, wherein Z is —NHL, L is trifluoroacetyl, —SO₂—CH₃ or—SO₂—CF₃, c is 1 to 4, a is 1, and b is
 1. 21. The method of claim 9,wherein Ar is an unsubstituted phenylene.